Amino derivatives and process of preparing them



Patented Oct. 8, 1935 "UNITED STATES AMINO DERIVATIVES AND rnocsss or PREPARING THEM William Stansfield Calcott, Pennsgrove, N. J., and

Richard Gesse Clarkson, Wilmington, DeL, assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application November 4, 1932, Serial No. 641,322

11 Claims. (Cl. 260-127) facture thereof. It further relates to a method for increasing the detergent power of treatment liquids, especially such as are employed in the textile and leather industries.

As is well known, various substances, such, as, for example, ordinary soaps, that is, the alkali metal salts of the higher fatty acids, are effective in increasing the detergent power and likewise the wetting and penetrating power of neutral aqueous treatment liquids or baths. Such substances are particularly useful in the textile and leather industries. In these industries, however, it may be desirable to treat certain materials with alkaline or acidic baths. In the textile industry, certain types of baths are much more efiective for the treatment of specific kinds of fabrics than are others. Thus, in cleaning woolen fibers it is advantageous to use mildly acidic treatment baths, sinc such fibers may be detrimentally affected by alkalies.

Ordinary soaps are of little value for use in acidic baths, since the alkali metal salts are converted to the insoluble fatty acids. Moreover, heavy metal or alkaline earth metal salts of higher'fatty acids are relatively insoluble in aqueous solutions. Hence, where hard wate containing salts of magnesium, calcium, and the like is used in aqueous treatment baths, and soaps are added thereto, a relatively large proportion of the soap may be precipitated.

It is an object of the present invention to produce new chemical compounds. A further object is to produce new chemical compounds which are valuable detergent agents, exerting excellent cleansing properties even in the presence of large amounts of acids or salts of heavy or alkaline earth metals. A still further object is the production of new and improved treatment liquids which are especially useful in the textile industry. Another and more specific object is the provision of a method for cleaning woolen fibers and fabrics by means of aqueous acidic treatment baths. A further object is the provision of a new and improved process for producing chemical compounds and treatment liquids of the character above described. Other objects will appear hereinafter.

These objects are accomplished by producing chemical compositions having the formula:

and acid addition products thereof, wherein n is 5 or 6, R1 is a higher aliphatic radical, having 8 or more carbon atoms, and R2 is hydrogen or an hours. water and neutralized with hydrochloric acid aliphatic radical. These products may be obtained in a variety of ways but preferably by combining an alkyl halide with an amine having the formula in which n is 5 or 6, X is hydrogen, and Y is hydrogen or an aliphatic radical. The resultant product may be further treated with an acid to form an acid addition product (salt) of the amine. Water-soluble compounds of the class described have been found to possess excellent detergent power in aqueous non-alkaline solutions.

While the invention is susceptible of considerable variation and modification in the manner of its practical application, particularly as regards the specific materials used, the proportions thereof and the method of their preparation, the following examples, in which the parts are by weight, will serve to illustrate some of the products falling within the invention and how they may be prepared.

Example I A mixture consisting of 15 parts of N-glucyl methyl amine, 24 parts of cetyl chloride (obtained from cetyl alcohol, zinc chloride and hydrochloric acid), 12 parts of sodium carbonate, 30 parts of a mixture containing equal proportions of alcohol and. benzene. and a trace of potassium iodide was charged into a copper-lined autoclave and maintained at a temperature of about C. for five hours. The reaction mixture was then treated with a, large volume of ethyl alcohol, and the inorganic salts which precipitated were removed by filtration. The product comprising substantially N-glucyl-N-methyl cetyl amine was obtained as a cream-colored solid by evaporating the alcoholic filtrate to dryness.

Example II 43.5 parts of the N-glucyl-N-methyl cetyl amine, produced as in Example I, we're treated with 10 parts of 37% hydrochloric acid at room temperature, and the resultant addition produci was recovered as a resinous solid with a neutrai reaction.

Example III A copper-lined autoclave was charged with 2 mixture consisting of 15 parts of N-glucyl methyl amine, 30 parts of lauryl bromide (made iron lauryl alcohol and hydrobromic acid), 12 part. of sodium carbonate, 30 parts of a 1:1 alcoholbenzene mixture, and a trace of potassium io dide and heated at about 150 C. for about 4 The reaction mixture was dissolved it It was concentrated to a small volume, a largl volume of ethyl alcohol added, and the inorganic salts removed by filtration. Evaporation of the aqueous alcohol solution yielded the hydrohalide of the N-glucyl-N-methyl lauryl amine as a brownish mass.

' Example IV A reaction mixture consist-ing of 10 parts of glucyl amine, 15 parts of cetyl chloride, 5 parts of sodium carbonate and a trace of potassium iodide in 50 parts of an aqueous alcohol mixture was heated at about 150 C. for about 5 hours. The reaction mixture was treated with water and neutralized with hydrochloric acid. The insoluble portion which was most probably NzN-dicetyl-glucyl amine was removed by filtration. The filtrate was concentrated to a small volume, a large volume of ethyl alcohol added, and the inorganic salts were separated by evaporation of the aqueous alcohol solution. A brownish mass consisting principally of the hydrochloride of N-, glucyl cetyl amine was obtained.

Example V About 15 parts of the N-glucyl-N-methyl cetyl amine obtained ,as described in Example I, was treated with about 17 parts of 10% sulfuric acid to form the sulfuric acid addition product or salt of N-glucyl-N-methyl cetyl amine.

Erample VI -The product of Example I was added to distilled water and the resultant treatment bath was tested by washing woolen felt, oiled as described by Rhodes and Brainard, Journal of Industrial and Engineering Chemistry, 21, 60 (1929) in an ordinary launderometer and judging the degree of cleanliness optically. N-glucyl-N-methyl cetyl amine was found to be as effective a detergent as soap in distilled.- water at the same concentration.

Example VII A treatment bath was prepared by adding 25 parts of the product of Example I to 10,000 parts of water containing about 4 parts of calcium chloride, and the resultant liquid was tested for detergent power as described in Example VI. It was found that the N-glucyl-N-methyl cetyl amine was as eifective in the calcium chloride solution as in distilled water, whereas soap gave no cleansing whatever.

Example VIII Example IX The product of Example II was tested as in Example VI and was found to have good detergent power but to be slightly less effective as a detergent than the product of Example 1. Its action was not decreased by the presence of mineral acids or calcium chloride.

According to the general procedure of Examples I to V inclusive, a similar process can be carried out by using in place of a glucyl amine,

any other sugaramine in which the mono-sac charide radical contains 5 or 6 carbon atom: The amines may be prepared in any suitabl manner from mono-saccharides of the ketose o aldose type containing 5 or 6 carbon atoms Thus, instead of a glucyl amine, that is, an amim prepared from glucose, amines prepared from arabinose, ribose, lyxose, xylose, gulose, mannose idose, allose, galactose, altrose, talose, d'fruc tose and the like may be used. A method of pre paring such amines is described in a co-pendim application of Robert B. Flint and Paul L. Salz berg, Serial No. 635,045, in which sugars c'ontaining 5 or 6 carbon atomsare reacted with a pri' mary or secondary amine and hydrogen unde: elevated pressure and at an elevated temperatun in the presence of a, hydrogenating catalyst. In eluded among the specific products described arq N-methyl-glucamine, N-methyl-xylamine, N-butyl-xylamine, N-ethyl-glucamine, N-hydroxy' ethyl-glucamine,N-methyl-galactamine, N-meth yl-fructamine and the like. Any of the prima'r: or secondary amines of the character describe are applicable for use in the present inventior as starting materials. a

The method of combining the primary or secondary amine with the alkyl halide to form tht new secondary or tertiary amines is subject t considerable variation and may vary widely 1: details of a character well known inthe art. The process is preferably carried out by reacting the primary or secondary amine and the alkyl halide in the presence of an acid-binding agent as, for example, sodium carbonate, magnesium oxide calcium carbonate, potassium carbonate, potassium acetate, sodium acetate, and the like. It i:

- preferable also to effect the reaction in a solvent such as, for example, an alcohol-benzene mixture or an aqueous alcohol solution. In general, any inert solvent may be used. It is further desirable to employ a condensation catalyst such as. for example potassium iodide or sodium iodide.

The proportions of alkyl halide, primary or secondary amine, acid-binding agent, solvent and catalyst may vary within relatively wide limits depending largely upon the results desired. Generally speaking, it is desirable to use atleast a sufficient amount of the acid-binding agent to react with all of the hydrogen halide'liberated by the reaction.

The temperature may vary within relatively wide limits, but should preferably be sufficiently high to enable the reaction to proceed smoothly and quickly but insufliciently high to cause the formation of decomposition products. In general temperatures within the range of about C. to 200 C. give desirable results.

In the formation of the acid addition products (salts) of the new secondary and tertiary amines, the secondary and tertiary amines may be combined with any suitable acids, as for example, hydrochloric, sulfuric, phosphoric, acetic and formic.

In general, the products which are preferably employed as detergents are those which have the formula and acid addition products thereof, wherein n is 5 or 6, R1 is a radical having 8 or more carbon atoms (e. g., capryl, lauryl, myristyl, cetyl, stearyl (CisHsv), cerotyl, oleyl (C1aH35), erueyLlinoleyl, lin'olenyl, ricinoleyl, and the like) and R2 is hydrogen or an aliphatic radical such that the compound is water-soluble (e. g., methyl, ethyl, propyl, butyl, allyl, hydroxy ethyl, dihydroxy propyl, and substituted aliphatic radicals containing as substituents such groups as the sulfate or sulfonic acid groups). Very highly advantageous results have been obtained in the .use of compounds having the foregoing general formula, in which the poly-hydroxy aliphatic radical is a normal radical having 6 carbon atoms, ,and the following general formula ,(generally referred to as the glucyl group); It is further desirable that the compound be one in which, according to the general formula, R1 is a straight chain or normal alkyl radical having 8 or more carbon atoms. For the application of the products as detergents in aqueous baths, it is preferable that R: of the general formula be a lower aliphatic radical, preferably an alkyl radical containing not more than 4 carbon atoms (cf. Examples I, II and III) or a substituted alkyl radical containing not more than 4 carbon atoms, as for example, N-cetyl-N-glucyl ethanolamine, or N-cetyl-N-glucyl-2:3-propane diol-l-amine.

I'he new class of compounds described may be used in cleansing materials of all kinds and, as previously indicated, are particularly valuable for use in acidic aqueous solutions or aqueous solutions containing metallic salts in which ordinary soaps are ineifective. While the invention is not; limited to any theory, it is believed that the excellent properties of the products and the advantages they possess over ordinary soaps can be traced to the fact that these new products contain no carboxyl groups on the long chain alkyl group, such as is the case with ordinary soaps. Apparently, another reasonwhy these products have given such good results lies in the fact that they contain the amino group, the acid salts of which have a neutral or slightly acid reaction rather than a slight alkaline reaction as in the case of soaps. Because of their great effective cleansing power in acidic solutions, the new products are particularly valuable in cleaning silk, wool and other materials which are detrimentally affected by alkaline solutions, but which may be cleaned in acidic solutions.

The treatment baths prepared in accordance with the invention may contain, in addition to the products herein described, other compounds which are surface active or possess cleaning, wetting, penetrating or dispersing properties. examples of additional materials possessing washing, cleansing, emulsifying and wetting power may be mentioned Turkey red oils, ordinary soaps (in neutral solutions), aromatic sulfonic acid (such as alkylated naphthalene sulfonic acids), mineral oil sulfonic acids, sulfonated derivatives of abietic acid, higher alkyl sulfuric esters, saponin, and aliphatic and aromatic acid amides, such as sodium taurocholate or sodium salts of analogous acid amides. The products of the invention may also'be employed in combination with neutral or acid salts, such as, for example, sodium sulfate, sodium chloride, sodium bisulfate, sodium bicarbonate, and similar compounds of the other alkali metals or of ammonium. In a like manner, they may be employed with magnesium sulfate, magnesium chloride, magnesium acetate, zinc chloride and zinc acetate.

Other additional materials with which the products of the inventionmay be combined are bleaching andedisinfectant agents, 'such as per;- sulfates, percarbonates and perborates; filling materials such as. talc, marble-dust and starch; adsorbing materials'such as suitable clays, e. g.,

fuller's earth;- protective colloids or dispersing agents such as gum tragacanth, .gall acidsand their derivatives, agar-agar, glue, methyl cellulose, sulflte cellulose lyes, calcium saccharate, albumin, sodium celluloseglycollate, gelatin, na- 1. tural and artificial resins, derivatives ofoholem terine, phosphatides, gelloses, natural and artificial waxes, wool waxes, solvent and softening agents, organic bases-and -their"salts such as alkylolamine salts and quaternary ammonium 14 compounds. inorganic colloids; and scouring ma-. terials such as kieselguhr, powdered pumice, sulfur, flour, china clay, salt and the like. Desirable results for many purposes may also be obtained by employing the secondary or tertiary amines .or.2| salts thereof, produced as herein described, 'in' combination with the various acyclic,'mono-cyclic or complex cyclicterpenesor derivatives thereof such as, for example, limonene, dipentene, terpinolene, terpinene, phellandrene, sylvestrene, 21 pinene, borynlene, sabinene and their alcoholic, kctonic and aldehydic derivatives. It will be ap} parent, furthermore, that our. newproducts may be combined with a wide variety of other addi tional materials which possess washing, cleans} 31 ing. emulsifying, wetting, dispersing, adsorbing, lathering. bleaching, germicidal and bactericidal powers. They may likewise have incorporated therewith artificial or natural per-fuming substances, many of which .in1 themselves possess at detergent properties of some value.

As many apparently widely diif erent e nbodk ments of this invention may be' made without departing from the spirit and scope thereoL it is to be understood that we do not limit our- 4! selves to the specific embodiments thereof ex-' cept as definedin thefol1owin'gjclaim sj We claim:

1. In a process of producing chemical compounds having the following formula R: wherein 12, is 5 or 6, R1 is an aliphatic radical having an open chain of at least eight carbon atoms, and R2 is hydrogen or an aliphatic radical, the step which comprises reacting an amine having the formula amine having the formula 65 in which n is 5 or 6, X is hydrogen, and Y is hydrogen or an aliphatic radical, with an alkyl halide having at least eight carbon atoms, and further combining the resultant product with an 7 acid. I

3. In a process of producing chemical compounds having the following formulawherein n is 5 or 6, R1 is an alkyl radical having at least eight carbon atoms, and R2 is hydrogen or an aliphatic radical such that the compound is water-soluble, the step which comprises reacting an amine having the formula x I)( )UI( )B+I in which n is 5 or 6, X is hydrogen, and Y 'is hydrogen or a lower aliphatic radical, with an alkyl halide having at least eight carbon atoms. 4. In a process of producing new chemical compounds, the step which comprises reacting an amine having the formula x H)( )n-l( )n+I N I Y in which n is 5 or 6, X is hydrogen, and Y is hydrogen or a lower aliphatic radical, with an aliphatic halide having at least eight carbon atoms, and further combining the resultant product with an acid.

5. Compounds of the group consisting of compounds having the following formula R l n)( )n-l( )|H-T Ba and the acid addition products thereof, in which n is 5 or 6, R1 is an aliphatic radical having an open chain of at least eight carbon atoms, and R: is hydrogen or an aliphatic radical.

6. Compounds of the group consisting of compounds having the following formula and the acid addition products thereof, in whichn is 5 or 6, R1.is an alkyl radical having at least eight carbon atoms, and R2 is hydrogen or an aliphatic radical such that the compound is water-soluble.

7. Compounds of the group consisting of compounds having the following formula I /Ri and the acid addition productsthereof, in which n is 5 or 6, R1 is an alkyl radical having at least eight carbon atoms, and R: is hydrogen, an alkyl radical having not more than four carbon atoms, or a hydroxy alkyl radical having not more than four carbon atoms.

8. A compound having the following general formula:

HHHHE of the alkyl radicals is a higher alkyl radical containing at least eight carbon atoms and the other is a lower alkyl radical having not more than four carbon atoms.

WILLIAM s. CALCOTT. rennan G. CLARKSON.

. Certificate of Correction Patent No. 2,016,956; v October 8, 1935. WILLIAM STANSFIELD CALCOTT ET AL.

'It is hereby certified 'thet errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 33, for oiled read soiled; and page 4, first column, line 45, for R read R and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of. the case in the Patent Ofiice.

' Signed and sealed this 17th day of December, 1935.

eel] v [S LESLIE FRAZER,

Acting Commissioner of Patents. 

